CN102208683A - Electrolyte for improving high-temperature storage performance of lithium-ion secondary battery - Google Patents
Electrolyte for improving high-temperature storage performance of lithium-ion secondary battery Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 96
- 238000003860 storage Methods 0.000 title claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 30
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 23
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 18
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 11
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 8
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 5
- 229910013188 LiBOB Inorganic materials 0.000 claims description 5
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 4
- 229930188620 butyrolactone Natural products 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 239000006259 organic additive Substances 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 claims description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 229960002645 boric acid Drugs 0.000 claims description 2
- 235000010338 boric acid Nutrition 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000007784 solid electrolyte Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- -1 sulfonate group class lithium salts Chemical class 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 230000006399 behavior Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
Abstract
The invention relates to an electrolyte for improving the high-temperature storage performance of a lithium-ion secondary battery, comprising a lithium salt, an organic solvent and an additive. The electrolyte is characterized in that the electrolyte also comprises a high-temperature film-forming agent; and the high-temperature film-forming agent is selected one or two between methylene methanedisulfonate and propone-1,2-cyceic suefite1,2-propanediol sulfit. The high-temperature film-forming agent is applied to the electrolyte, so that a solid electrolyte film with good heat stability can be formed on a graphite negative pole of the lithium-ion secondary battery, thus overcoming the defects that an existing lithium-ion secondary battery is quick in loss of storage capacity and low in recovery rate under the condition of high temperature. The electrolyte is reasonable in proportion, remarkable in effect and wide in application, and can preferably meet demands of consumers for the high-temperature performance of the battery.
Description
Technical field
The present invention relates to a kind of electrolyte, especially the electrolyte of lithium rechargeable battery.
Background technology
Along with being extensive use of of products such as digital product such as mobile phone, notebook computer, lithium rechargeable battery is used widely in this series products with its excellent performance, and is progressively developing to other product applications in recent years.Along with the expansion of lithium rechargeable battery application, the high-temperature storage and the storage back chemical property of lithium ion battery are had higher requirement.
The media that electrolyte transmits between both positive and negative polarity as lithium ion, the quality of its performance directly influence the chemical property after lithium rechargeable battery stores and stores.
Chinese patent 200910102144.7 discloses a kind of electrolyte, removes to contain organic solvent and lithium salts electrolyte, also contains the component of sulfonate group class lithium salts.This scheme is by adding electrolyte, make full electric attitude high temperature 60 degree of battery store 24 hours, the increase of integral battery door thickness is no more than 5%, the integral battery door capability retention surpasses 95%, recovery rate surpasses 98%, but the sulfonate group class lithium salts that this scheme adopts, complex structure, the manufacturing cost height, the scope of application is little.
Chinese patent 201010181766.6 discloses a kind of high-temperature electrolyte of lithium ion battery, add ammonium salt in the electrolyte as additive, the ammonium ion that ammonium salt ionization is come out hinders the deposition of metal ion on negative pole of anodal stripping to a certain extent, thereby improve use and the storge quality of lithium ion battery under hot environment, but the ammonium ion less stable that ammonium salt ionization is come out, high temperature or chance alkali easily decompose.
Chinese patent 200910147183.9 provides a kind of lithium-ion battery electrolytes and preparation method who is applicable to hot environment, electrolyte is made up of lithium salts, organic solvent and additive, wherein the quality proportioning is respectively: lithium salts 11% ~ 16%, organic solvent 81% ~ 88%, additive 1% ~ 3%.The additive that is added in the electrolyte is propane sultone (PS), vinylene carbonate (VC), vinylethylene carbonate (VEC), LiBF4 (LiBF
4), this electrolyte satisfies lithium ion battery after 90 degree stored in 4 hours, the internal resistance of battery increases less than 3 milliohms, the capacity residue is greater than 90%, and after recovering the normal temperature discharge, discharge capacity is suitable before discharge capacity and the storage, although the electrolyte that this patent provides has improved the high temperature storage of lithium ion battery, but this electrolyte high temperature was stored for more time as 24 hours, and its capability retention and recovery rate are still lower, can not satisfy the demand of consumer to battery high-temperature behavior.
In sum, the existing aluminum hull lithium rechargeable battery state of the art is: full electric attitude high temperature 75 degree store 24 hours, and the increase of integral battery door thickness surpasses 10%, and the integral battery door capability retention is no more than 90%, and recovery rate is no more than 95%.
Summary of the invention
Shortcomings such as it is fast to the objective of the invention is to overcome under the existing lithium rechargeable battery hot conditions memory capacity loss, and recovery rate is low provide a kind of electrolyte, can effectively improve the high-temperature storage performance of lithium rechargeable battery.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs: a kind of electrolyte that improves the lithium rechargeable battery high-temperature storage performance, and this electrolyte contains lithium salts, organic solvent and additive, also contains the high temperature film forming agent in the described electrolyte; Described high temperature film forming agent is one or both in methane-disulfonic acid methylene ester, the 4-methyl glycol sulfite.
As preferably, described high temperature film forming agent is methane-disulfonic acid methylene ester, 4-methyl glycol sulfite, and both mass ratioes are: 3:2.
Described additive is one or more in propylene sulfite, propane sultone, ethyl sulfate, the sulfuric acid propylene ester.
The quality percentage composition that described additive accounts for the electrolyte total amount is 0.5% ~ 10%.
The quality percentage composition that described high temperature film forming agent accounts for the electrolyte total amount is 0.5% ~ 10%.
Described lithium salts can be preferably lithium hexafluoro phosphate (LiPF for well known to a person skilled in the art the various lithium salts that are used for lithium rechargeable battery
6), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), LiBF4 (LiBF
4) in one or more.Described lithium salt is 0.8mol/L ~ 2.0mol/L.
Described organic solvent can be for well known to a person skilled in the art various organic solvents, is preferably in ethylene carbonate (EC), propene carbonate (PC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), carbonic acid first propyl ester (MPC), the butyrolactone (GBL) one or more.
The quality percentage composition that each composition accounts for the electrolyte total amount in the described organic solvent is respectively: ethylene carbonate is 10% ~ 60% wt, propene carbonate is 0% ~ 60% wt, methyl ethyl carbonate is 0%-60% wt, diethyl carbonate is 0% ~ 60% wt, it is 0% ~ 60% wt that carbonic acid first propyl ester accounts for, and butyrolactone is 0% ~ 60% wt.
As of the present invention a kind of preferred, described electrolyte is composed as follows: lithium salts LiPF
6Concentration is 1.0mol/L, organic solvent EC/EMC/PC=1/2/1(mass ratio), the quality percentage composition that additive accounts for the electrolyte total amount is 1%, the quality percentage composition that the high temperature film forming agent accounts for the electrolyte total amount is 0.5%.
As of the present invention a kind of preferred, described electrolyte is composed as follows: lithium salts: LiPF
6, LiODFB concentration is respectively 1.2mol/L and 0.2mol/L, organic solvent EC/EMC/DEC=1/2/1(mass ratio), the quality percentage composition that additive accounts for the electrolyte total amount is 2%, the quality percentage composition that the high temperature film forming agent accounts for the electrolyte total amount is 5%.
As of the present invention a kind of preferred, described electrolyte is composed as follows: lithium salts: LiPF
6, LiBOB, LiODFB concentration be respectively 1.2mol/L, 0.2mol/L and 0.2mol/L, organic solvent EC/EMC/DEC/PC=1/2/2/1(mass ratio), the quality percentage composition that additive accounts for the electrolyte total amount is 5%, and the quality percentage composition that the high temperature film forming agent accounts for the electrolyte total amount is 10%.
As of the present invention a kind of preferred, described electrolyte is composed as follows: lithium salts LiPF
6And LiBF
4Concentration is respectively 1.2mol/L and 0.4mol/L, organic solvent EC/MPC/GBL=2/1/3(mass ratio), the quality percentage composition that additive accounts for the electrolyte total amount is 1%, the quality percentage composition that the high temperature film forming agent accounts for the electrolyte total amount is 5%.
As of the present invention a kind of preferred, described electrolyte is composed as follows: lithium salts LiPF
6Be respectively 1.4mol/L and 0.4mol/L with LiODFB concentration, organic solvent is EC/EMC/ PC=2/3/2(mass ratio), the quality percentage composition that additive accounts for the electrolyte total amount is 3%, the quality percentage composition that the high temperature film forming agent accounts for the electrolyte total amount is 10%.
As of the present invention a kind of preferred, described electrolyte is composed as follows: lithium salts LiPF
6Concentration is respectively 1.4mol/L, organic solvent EC/EMC=2/3(mass ratio), the quality percentage composition that additive accounts for the electrolyte total amount is 3%, the quality percentage composition that the high temperature film forming agent accounts for the electrolyte total amount is 5%.
The invention has the beneficial effects as follows: by in electrolyte, using the high temperature film for additive, can form the solid electrolyte film of excellent heat stability at the lithium rechargeable battery graphite cathode, overcome under the existing lithium ion battery hot environment use and the memory capacity loss soon, the shortcoming that recovery rate is low, make battery 75 ℃ of storages of full electric attitude high temperature 24 hours, the increase of integral battery door thickness is no more than 2%, and the integral battery door capability retention is more than 95%, and the capacity restoration rate is more than 98%.Electrolyte ratio of the present invention is reasonable, and effect is remarkable, is widely used, and can satisfy the demand of consumer to battery high-temperature behavior well.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
Electrolyte is composed as follows: lithium salts LiPF
6Concentration 2.0mol/L, organic solvent EC/EMC/PC=1/2/1(mass ratio), the quality percentage composition that additive PS accounts for the electrolyte total amount is 1%, the quality percentage composition that high temperature film forming agent methane-disulfonic acid methylene ester accounts for the electrolyte total amount is 0.5%.
Embodiment 2
Electrolyte is composed as follows: lithium salts: LiPF
6, LiODFB concentration is respectively 1.2mol/L and 0.3mol/L, organic solvent EC/EMC/PC=1/2/1(mass ratio), the quality percentage composition that additive PS accounts for the electrolyte total amount is 0.5%, and the quality percentage composition that high temperature film forming agent 4-methyl glycol sulfite accounts for the electrolyte total amount is 5%.
Embodiment 3
Electrolyte is composed as follows: lithium salts: LiPF
6, LiBOB, LiODFB concentration be respectively 1.2mol/L, 0.2mol/L and 0.2mol/L, organic solvent EC/EMC/DEC/PC=1/2/2/1(mass ratio), the quality percentage composition that the quality percentage composition that the additive propylene sulfite accounts for the electrolyte total amount is 2%, PS accounts for the electrolyte total amount is 3%, and the quality percentage composition that the quality percentage composition that high temperature film forming agent methane-disulfonic acid methylene ester accounts for the electrolyte total amount is 3%, 4-methyl glycol sulfite accounts for the electrolyte total amount is 2%.
Embodiment 4
Electrolyte is composed as follows: lithium salts LiPF
6And LiBF
4Concentration is respectively 1.2mol/L and 0.4mol/L, organic solvent EC/MPC/GBL=2/1/3(mass ratio), the quality percentage composition that additive sulfuric acid ethyl accounts for the electrolyte total amount is 10%, and the quality percentage composition that high temperature film forming agent 4-methyl glycol sulfite accounts for the electrolyte total amount is 5%.
Embodiment 5
Electrolyte is composed as follows: lithium salts LiPF
6Be respectively 1.4mol/L and 0.4mol/L with LiODFB concentration, organic solvent is EC/ EMC/PC=2/3/2(mass ratio), the quality percentage composition that additive sulfur acid propylene ester accounts for the electrolyte total amount is 3%, and the quality percentage composition that the quality percentage composition that high temperature film forming agent methane-disulfonic acid methylene ester accounts for the electrolyte total amount is 5%, 4-methyl glycol sulfite accounts for the electrolyte total amount is 5%.
Embodiment 6
Electrolyte is composed as follows: lithium salts LiPF
6Concentration is 0.8mol/L, and organic solvent is the EC/EMC=2/3(mass ratio), the quality percentage composition that additive sulfur acid propylene ester accounts for the electrolyte total amount is 3%, the quality percentage composition that high temperature film forming agent 4-methyl glycol sulfite accounts for the electrolyte total amount is 5%.
Comparative example 1
Electrolyte is composed as follows: lithium salts LiPF
6Concentration is 1mol/L, organic solvent EC/EMC/PC=1/2/1(mass ratio), the quality percentage composition that additive VC accounts for the electrolyte total amount is 1.5%.
Comparative example 2
Electrolyte is composed as follows: lithium salts LiPF
6Concentration is 1.2mol/L, organic solvent EC/EMC/DEC=1/1/2(mass ratio), the quality percentage composition that additive PS accounts for the electrolyte total amount is 1%.
Comparative example 3
Electrolyte is composed as follows: lithium salts LiPF
6Concentration is 1.2mol/L, organic solvent EC/EMC/DEC/PC=1/2/2/1(mass ratio), the quality percentage composition that the additive propylene sulfite accounts for the electrolyte total amount is 3%.
Comparative example 4
Electrolyte is composed as follows: lithium salts LiPF
6Be respectively 1mol/L and 0.2 mol/L with LiBOB concentration, organic solvent EC/EMC/MPC/PC=1/1/1/2(mass ratio), the quality percentage composition that the additive propylene sulfite accounts for the electrolyte total amount is for being 2%.
Comparative example 5
Electrolyte is composed as follows: lithium salts LiPF
6Be 1mol/L, LiBF
4Be 0.4mol/L, organic solvent EC/EMC/MPC/PC=1/2/2/1(mass ratio), additive vinylethylene carbonate addition is 3%.
Adopt the electrolyte of embodiment 1 ~ 6 and comparative example 1 ~ 5, used Experimental cell is an aluminum-shell battery, and specifications and models are 643960AL, and electric core thickness is 6.4 millimeters, and length is 60 millimeters, and wide is 39 millimeters; Integral battery door nominal capacity 1800 MAHs.Integral battery door charges to 4.2 volts with the 1C multiplying power before storing, 4.2 volts of constant voltage charges to electric current smaller or equal to 36 milliamperes; Integral battery door places in the insulating box, and after 75 degree stored 24 hours, the 0.2C multiplying power was discharged to 3 volts, and discharge capacity is the maintenance capacity of integral battery door; After 3 weeks, the discharge capacity of integral battery door 0.2C multiplying power is the recovery capacity 0.2C rate charge-discharge circulates, and experimental data is as shown in the table:
Can adopt full electric attitude high temperature 75 degree of battery (comparative example 1 ~ 5) of the electrolyte of prior art to store 24 hours from last table 1, integral battery door thickness increases above 10%, and the integral battery door capability retention is no more than 90%, and recovery rate is no more than 95%.And the present invention overcome under the existing lithium ion battery hot environment use and the memory capacity loss soon, the shortcoming that recovery rate is low, make full electric attitude high temperature 75 degree of lithium rechargeable battery store 24 hours, the increase of integral battery door thickness is no more than 2%, the integral battery door capability retention is more than 95%, and the capacity restoration rate is more than 98%.Electrolyte ratio of the present invention is reasonable, and effect is remarkable, is widely used, and can satisfy the demand of consumer to battery high-temperature behavior well.
This specific embodiment only is an explanation of the invention; it is not a limitation of the present invention; those skilled in the art can make any modification to present embodiment as required after reading this specification, but as long as all are subjected to the protection of Patent Law in claim scope of the present invention.
Claims (9)
1. electrolyte that improves the lithium rechargeable battery high-temperature storage performance, this electrolyte contains lithium salts, organic solvent and additive, it is characterized in that: also contain the high temperature film forming agent in the described electrolyte; Described high temperature film forming agent is one or both in methane-disulfonic acid methylene ester, the 4-methyl glycol sulfite.
2. a kind of electrolyte that improves the lithium rechargeable battery high-temperature storage performance according to claim 1 is characterized in that: described additive is one or more in propylene sulfite, propane sultone, ethyl sulfate, the sulfuric acid propylene ester.
3. a kind of electrolyte that improves the lithium rechargeable battery high-temperature storage performance according to claim 2 is characterized in that: the quality percentage composition that described additive accounts for the electrolyte total amount is 0.5% ~ 10%.
4. a kind of electrolyte that improves the lithium rechargeable battery high-temperature storage performance according to claim 1 is characterized in that: the quality percentage composition that described high temperature film forming agent accounts for the electrolyte total amount is 0.5% ~ 10%.
5. a kind of electrolyte that improves the lithium rechargeable battery high-temperature storage performance according to claim 1 is characterized in that: described lithium salts is lithium hexafluoro phosphate (LiPF
6), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), LiBF4 (LiBF
4) in one or more.
6. a kind of electrolyte that improves the lithium rechargeable battery high-temperature storage performance according to claim 1 is characterized in that: lithium salt is 0.8mol/L ~ 2mol/L in the described electrolyte.
7. a kind of electrolyte that improves the lithium rechargeable battery high-temperature storage performance according to claim 1 is characterized in that: described organic solvent is one or more in ethylene carbonate (EC), propene carbonate (PC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), carbonic acid first propyl ester (MPC), the butyrolactone (GBL).
8. a kind of electrolyte that improves the lithium rechargeable battery high-temperature storage performance according to claim 1, it is characterized in that: the quality percentage composition that each composition accounts for the electrolyte total amount in the described organic solvent is respectively: ethylene carbonate is 10% ~ 60% wt, propene carbonate is 0% ~ 60% wt, methyl ethyl carbonate is 0% ~ 60% wt, diethyl carbonate is 0% ~ 60% wt, it is 0% ~ 60% wt that carbonic acid first propyl ester accounts for, and butyrolactone is 0% ~ 60% wt.
9. a kind of electrolyte that improves the lithium rechargeable battery high-temperature storage performance according to claim 1 is characterized in that: described high temperature film forming agent is methane-disulfonic acid methylene ester, 4-methyl glycol sulfite, and both mass ratioes are: 3:2.
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Cited By (10)
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|---|---|---|---|---|
| CN102769148A (en) * | 2012-06-21 | 2012-11-07 | 新乡市盛林能源有限公司 | High-power lithium ion battery electrolyte |
| CN103078136A (en) * | 2012-12-03 | 2013-05-01 | 湖州创亚动力电池材料有限公司 | Low-temperature rate lithium ion battery electrolyte |
| CN103855426A (en) * | 2012-12-06 | 2014-06-11 | 上海比亚迪有限公司 | Lithium ion battery electrolyte and lithium ion battery containing same |
| CN104810548A (en) * | 2014-07-15 | 2015-07-29 | 万向A一二三系统有限公司 | High-performance lithium titanate power battery |
| CN105489926A (en) * | 2014-10-08 | 2016-04-13 | 南通力合新能源有限公司 | Nonaqueous electrolyte additive capable of improving cycle pulse impedance of lithium ion battery |
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| CN103078136B (en) * | 2012-12-03 | 2015-04-22 | 湖州创亚动力电池材料有限公司 | Low-temperature rate lithium ion battery electrolyte |
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| CN103855426B (en) * | 2012-12-06 | 2016-03-02 | 上海比亚迪有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery containing this electrolyte |
| CN104810548A (en) * | 2014-07-15 | 2015-07-29 | 万向A一二三系统有限公司 | High-performance lithium titanate power battery |
| CN105489926A (en) * | 2014-10-08 | 2016-04-13 | 南通力合新能源有限公司 | Nonaqueous electrolyte additive capable of improving cycle pulse impedance of lithium ion battery |
| CN106602140A (en) * | 2015-10-23 | 2017-04-26 | 天津金牛电源材料有限责任公司 | Electrolytic solution for improving high temperature performance of polymer lithium ion secondary battery |
| CN106602140B (en) * | 2015-10-23 | 2019-06-28 | 天津金牛电源材料有限责任公司 | A kind of electrolyte improving polymer lithium ion secondary battery high-temperature behavior |
| CN107017431A (en) * | 2016-01-28 | 2017-08-04 | 宁德新能源科技有限公司 | Nonaqueous electrolytic solution and lithium ion battery |
| CN106410282A (en) * | 2016-10-19 | 2017-02-15 | 广州天赐高新材料股份有限公司 | Pretreatment agent and pretreatment method for high-nickel positive electrode of power lithium ion battery |
| CN109459463A (en) * | 2017-12-05 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of quick evaluation method of anode material for lithium-ion batteries hot storage stability |
| CN114006125A (en) * | 2021-10-29 | 2022-02-01 | 河北金力新能源科技股份有限公司 | High-temperature-storage-resistant oil-based lithium ion battery diaphragm and preparation method thereof |
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